EP0507426A1

EP0507426A1 - Process for dissolving polyurethane foams or removing them from substrates

Info

Publication number: EP0507426A1
Application number: EP19920300034
Authority: EP
Inventors: Edward Thomas Marquis; George Phillip Speranza; Wei Yang Su
Original assignee: Texaco Chemical Co
Current assignee: Huntsman Corp
Priority date: 1991-04-01
Filing date: 1992-01-03
Publication date: 1992-10-07
Also published as: CA2063362A1; US5183514A; JPH05171077A

Abstract

Flexible or rigid polyurethane foam may be dissolved, or removed from a substrate, by contact with a solvent formulation containing or consisting of a 1,2-dialkyl imidazole, preferably having the formula

wherein R¹ and R² are each alkyl having no more than 20 carbon atoms.

Description

The invention relates to solvents for dissolving cured and/or uncured polyurethane foams.
A variety of solvents has been used to clean polyurethane foam from processing equipment, metal parts and tools, both before and after the polyurethane foam has cured on them. Some of the solvents used include such compounds as dimethyl formamide, 1,1,1-trichloroethane, methylene chloride, chlorofluorocarbons, toluene, xylene, acetone, methyl ethyl ketone, ethylene glycol ethers, tetrahydrofuran, and gamma-butyrolactone. However, although these compounds are effective solvents, the use of each presents a hazard or complication of one type or another. For example, the chlorine-containing compounds are now thought to contribute to ozone depletion in the atmosphere. The other solvents are either toxic, suspected carcinogens, or very volatile, and thus present health and safety problems.
We have discovered, surprisingly, that polyurethane foam may be dissolved, or removed from a substrate, by contacting the polyurethane foam with a solvent comprising 1,2-dialkyl imidazole. The present invention, by substituting 1,2-dialkyl imidazole in whole or in part for the more hazardous prior art solvents, reduces many of the health, safety and environmental hazards associated with the prior art solvents.
One embodiment of the invention concerns a process for dissolving polyurethane foam, comprising contacting polyurethane foam with 1,2-dialkyl imidazole. In another embodiment, the invention concerns a process for removing polyurethane foam from a substrate, by contacting said polyurethane foam with a solvent formulation containing 1,2-dialkyl imidazole.
1,2-Dialkyl imidazoles useful in the present invention may be represented by the following formula:

where R¹ and R² are each an alkyl group. It is preferred that R¹ and R² each represent an alkyl group having no more than 20 carbon atoms. It is especially preferred (1) that both R¹ and R² are methyl i.e. that the 1,2-dialkyl imidazole is 1,2-dimethyl imidazole, or (2) that R¹ is an isopropyl group and R² is a methyl group, i.e. that the 1,2-dialkyl imidazole is 1-isopropyl-2-methyl imidazole. Alternatively, a mixture of 1,2-dialkyl imidazoles may be used. Some 1,2-dialkyl imidazoles are commercially available. Additionally, 1,2-dialkyl imidazoles may be prepared by the methods claimed in US-A-4921969 and -4927942.
The solvents for which 1,2-dialkyl imidazoles may be substituted, in whole or in part, include, but are not limited to, aromatic hydrocarbons, alcohols, ketones, esters, ethers, glycol ethers, alkylene carbonates and ureas. Examples of suitable co-solvents include one or more of the following: toluene, 2-ethyl-1-hexanol, ethylene glycol diacetate, 2-ethylhexyl acetate, N-methyl pyrrolidinone, tetrahydrofurfuryl alcohol, ethylene glycol butyl ether acetate, tetramethyl urea, diethylene glycol butyl ether, ethylene glycol butyl ether, methyl iso-amyl ketone, diethylene glycol methyl ether, dipropylene glycol methyl ether, dibasic ester, methyl isobutyl ketone, N,N'-dimethyl ethylene urea, propylene glycol methyl ether, cyclohexanone, diacetone alcohol, furfuryl alcohol, and isobutyl isobutyrate. Of course, the solvents for which 1,2-dialkyl imidazoles may be substituted, in whole or in part, include the more hazardous solvents mentioned at the beginning of the description. Optionally, other solvents may be added to the formulations of the present invention as well.
Preferably, the portion of conventional solvent replaced with 1,2-dialkyl imidazole in a formulation containing one or more conventional (non-1,2-dialkyl imidazole) solvents will be such that the 1,2-dialkyl imidazole and the conventional solvents in the formulation are present in a weight ratio of 1,2-dialkyl imidazole to total conventional solvent of 4:1 to 1:4, more preferably from 1:2 to 1:3. One skilled in the art may find other weight ratios to be optimum without departing from the scope of the present invention. Those skilled in the art will appreciate that the portion of conventional solvent(s) in a formulation which should be replaced with 1,2-dialkyl imidazole for a given polyurethane foam involves a balance of possible reduction in dissolution power, against the reduction or avoidance of additional expense and/or environmental, health and safety risks associated with the conventional solvents. Applicant has demonstrated the use of several different formulations in the examples that follow.
Optionally, other additives may be employed in the formulations used according to the present invention. For example, suitable thickeners may be included, such as ethylcellulose, hydroxypropyl cellulose, organic modified clay and hydrogenated castor oil,
Surfactants, to enhance the water washability of the substrate, may also be included. Suitable surfactants include potassium oleate, the dioctyl ester of sodium sulfosuccinic acid, sodium alkylnaphthalene sulfonate and sodium alkylbenzene sulfonate.
The process is effective at temperatures from room temperature to 100 °C and at pressures from atmospheric to several Megapascals. Optionally, the process of the present invention may be performed at an elevated temperature. While the process works well at room temperature, more rapid dissolution may be obtained by heating the 1,2-dialkyl imidazole-containing solvent formulation to a temeprature of 50 to 100°C. The solvent formulation may be applied to the polyurethane foam in any conventional manner. Typically, the polyurethane foam-coated substrate will be placed in a vat or sonic bath containing the solvent formulation. Alternatively, the sovlent formulation could be applied to the foam-coated substrate by brush or spray. The period of time for which the solvent.
formulation should be permitted to work undisturbed on the polyurethane foam to be removed will vary, after which, agitation of the surfaces to be cleaned of the foam via wiping, brushing or scraping is preferred.
Rigid polyurethane foam formulations are well known in the art and are commercially available. Rigid foams are more highly cross-linked than either elastomers or flexible foams. Other characteristics generally true of rigid polyurethane foams include (1) a structure having a high percentage of closed cells; (2) low thermal conductivity; (3) nonreversible deformability; (4) good load-bearing ability; and (5) high dimensional stability. Generally, rigid polyurethane foams are based on polyols having a molecular weight less than 1000, and more often from 400 to 800, and
a functionality of 2 to 8, and more typically from 4 to 8.
Flexible polyurethane foam formulations also are well known in the art and are commercially available. In contrast to rigid foams, flexible foams are not highly cross-linked. Other characteristics generally true of flexible polyurethane foams include (1) a structure having a high percentage of open cells; (2) air permeability; (3) reversible deformability; (4) a limited resistance to an applied load; and (5) low dimensional stability. Generally, flexible polyurethane foams are based on polyols having a molecular weight greater than 1000 (about 70 atoms or more per chain), and
a functionality of 2 to 4, and more typically of 2 to 3. The invention will be further illustrated by the following examples,

Examples

In the examples recorded in the Table below, the following procedure was used. Previously coated stainless steel 19 mm (3/4'') screw stock rods were wire brushed and cleaned with a solvent. Rods that had been coated with cured fiberglass were treated with acetone to remove any fiberglass residue; those that had been coated with cured flexible or rigid polyurethane foam were treated with methylene chloride. The rods were then sand blasted with micro beads. The rods were then coated with a rigid or flexible polyether-based foam formulation having the following components:

Rigid Foam
Component	Parts by Weight
Thanol® R-350-X	36.9
DC-193¹ (silicon surfactant)	0.5
R11 (trichlorofluoromethane)	15.0
TEXACAT® TD-33	0.3
Rubinate M² (polymeric isocyanate)	49.6

¹Dow Corning; ²ICI.

Flexible Foam
Component	Parts by Weight
Thanol® SF-5505¹	60.0
Niax® 34-28 Polymer Polyol²	40.0
Deionized Water	3.5
Diethanolamine	1.5
Silicon Oil L-5309³	1.5
TEXACAT®-33A⁴ (33 % TEDA in DPG)	0.5
UL-1 (organotin in cmp.)⁵	0.0065
Toluene diisocyanate	44.5

¹Arco; ²Union Carbide; ³Union Carbide; ⁴Texaco Chemical Co.; ⁵Witco Fomrez®.

The foams were then allowed to cure for two days or more before dissolution studies were begun. Each coated stock rod was then suspended in a beaker from a ring stand. Each beaker contained one of the solvent formulations recorded in the table below. At the bottom of each beaker was a stirring bar. After 16 to at room temperature,the rods were observed,and the approximate percentage of polyurethane foam removed by each formulation was estimated and recorded.

Ex. No.	Foam Type	Solvent System Components	Weight Ratio of Components	Approximate % Foam Removed
1	Cured Flexible	1-isopropyl-2-methyl imidazole	All	100 %
2	Cured Flexible	N,N-dimethylformamide	All	100 %
3	Cured Rigid	1,2-dimethyl imidazole	All	100 %
4	Cured Rigid	N,N-dimethylformamide	All	100 %
5	Cured Rigid	PC/1,2-dimethyl imidazole	70/110	60 %
6	Cured Rigid	PC/1,2-dimethyl imidazole	90/90	50 %
PC = Propylene carbonate.

Claims

A process for dissolving polyurethane foam, by contacting polyurethane foam with a solvent, characterised in that the solvent comprises a 1,2-dialkyl imidazole.
A process according to Claim 1 characterised in that the 1,2-dialkyl imidazole has the formula:
wherein R¹ and R² are each alkyl having no more than 20 carbon atoms.
A process according to Claim 1 or 2 characterised in that the 1,2-dialkyl imidazole is 1,2-dimethyl imidazole or 1-isopropyl-2-methyl imidazole.
A process according to any one of Claims 1 to 3 characterised in that the polyurethane foam is a rigid polyurethane foam.
A process according to any one of Claims 1 to 3 characterised in that the polyurethane foam is a flexible polyurethane foam.
A process according to Claim 5 or 6 characterised in that the polyurethane foam is a polyether-based polyurethane foam.
A process according to any one of Claims 1 to 6 characterised in that the 1,2-dialkyl imidazole is employed together with a second solvent in which said polyurethane foam is at least partially soluble.
A process according to Claim 7 characterised in that the second solvent is an aromatic hydrocarbon, alcohol, ketone, ester, ether, glycol ether, alkylene carbonate, or urea.
A process according to Claim 7 or 8 characterised in that the second solvent is toluene, 2-ethyl-1-hexanol, ethylene glycol diacetate, 2-ethylhexyl acetate, N-methyl pyrrolidinone, tetrahydrofurfuryl alcohol, ethylene glycol butyl ether acetate, tetramethyl urea, diethylene glycol butyl ether, ethylene glycol butyl ether, methyl iso-amyl ketone, diethylene glycol methyl ether, dipropylene glycol methyl ether, dibasic ester, methyl isobutyl ketone, N,N'-dimethyl ethylene urea, propylene glycol methyl ether, cyclohexanone, diacetone alcohol, furfuryl alcohol, or isobutyl isobutyrate.
A process according to any one of Claims 1 to 9 characterised in that the polyurethane foam is dissolved to remove it from a substrate.